EP0286034B1 - Use of surfactants in alumina precipitation in the bayer process - Google Patents

Use of surfactants in alumina precipitation in the bayer process Download PDF

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Publication number
EP0286034B1
EP0286034B1 EP88105315A EP88105315A EP0286034B1 EP 0286034 B1 EP0286034 B1 EP 0286034B1 EP 88105315 A EP88105315 A EP 88105315A EP 88105315 A EP88105315 A EP 88105315A EP 0286034 B1 EP0286034 B1 EP 0286034B1
Authority
EP
European Patent Office
Prior art keywords
oil
surfactant
alumina trihydrate
fatty acid
precipitation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88105315A
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German (de)
English (en)
French (fr)
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EP0286034A1 (en
Inventor
David O. Owen
David C. Davis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
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Publication date
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Application filed by Nalco Chemical Co filed Critical Nalco Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
    • C01F7/145—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process characterised by the use of a crystal growth modifying agent other than aluminium hydroxide seed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
    • C01F7/47—Purification of aluminium oxide, aluminium hydroxide or aluminates of aluminates, e.g. removal of compounds of Si, Fe, Ga or of organic compounds from Bayer process liquors
    • C01F7/473—Removal of organic compounds, e.g. sodium oxalate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • This invention is concerned with treatment of a Bayer process green liquor from which aluminum values are precipitated.
  • Bayer process liquor crystallization and precipitation of solubilized alumina trihydrate values from caustic liquors
  • Bayer process liquor is a critical step towards the economic recovery of aluminum values.
  • Bayer process operators optimize their precipitation methods so as to produce the greatest possible yield from the Bayer process liquors while trying to achieve a given crystal size distribution. It is desirable in most instances to obtain relatively large crystal size since this is beneficial in subsequent processing steps required to produce aluminum metal. Production is often limited by processing conditions under which the crystallization and precipitation is conducted. These processing conditions vary from one plant to the next and include, but are not limited to, temperature profiles, seed charge, seed crystal surface area, liquor loading, liquor purity, and the like.
  • sodium oxalate In addition to humate chemicals derived from the impure Bauxite ores, another primary organic contaminant is sodium oxalate, thought to be produced during the high temperature digestion of the raw material Bauxite ore in highly concentrated caustic solutions. Regardless of the source of sodium oxalate, its presence in Bayer process liquors is undesirable for a number of reasons, as explained in U.S. Patent No. 4,608,237.
  • Sodium oxalate often crystalizes and co-precipitates from solution over essentially the same temperature profiles as does the desired alumina trihydrate crystals.
  • Fine oxalate particles act as secondary nucleation sites for alumina trihydrate, thereby increasing the total number of alumina crystals during the alumina trihydrate precipitation. This has an effect of causing a shift to smaller alumina trihydrate crystal size distribution and the production of very finely divided materials which for the most part are not wanted.
  • some of the smaller size alumina trihydrate is needed, as will be explained.
  • the general criterion is not to produce any more of the fine particle crystal than is needed for reseeding.
  • the oxalate crystals which are extremely finely divided and have an extremely large surface area, adhere to the surfaces of growing alumina trihydrate agglomerates. This adhesion of the oxalate crystalites interferes with both alumina trihydrate unit crystal growth and the agglomeration of alumina hydrate crystals. Occlusion of sodium oxalate crystalites within the growing alumina trihydrate multicrystal also results in the weakening of the final crystal structure. As noted above, this is very undesirable since it leads to the development of excessive amounts of extremely finely divided alumina trihydrate both during the precipitation process as well as in the alumina trihydrate calcination processes which follow.
  • German patent 636 707 is concerned with an alumina trihydrate precipitation process by means of carbon dioxide introduction wherein a small amount of mineral oil is added and the precipitation rate is increased.
  • Use of a surfactant-in-oil combination is neither anticipated nor suggested.
  • example 8A of the present specification the addition of mineral seal oil alone does not result in any percent reduction of small-sized crystals.
  • Bayer process pregnant or green liquors at different plants were employed to determine if the invention was in any way limited by variations in precipitation parameters employed by different producers of aluminum, known only to them. These parameters include the nature of the ore, the amount of impurities whether organic or inorganic, caustic concentrations, and especially the conditions inside the precipitation tank which include the form and purity of the seed crystals (small particles of alumina trihydrate), the degree of agitation, time, temperature, and so on. While the details of the precipitation techniques at the various plants are not known, it is known that they do vary widely.
  • the preferred surfactant is tall oil fatty acid, but there are a host of equivalents.
  • the fatty acid is one having at least a saturated or unsaturated four carbon alkyl backbone, with or without one or more carboxylic acid, ester, anhydride or sulfate surfactant functional groups attached directly or by a succinic alkyl linkage.
  • the fatty acid may contain at least an eight carbon backbone with at least one of the above functional groups attached.
  • the oil carrier may vary widely; the surfactants are oil soluble and there are many oils with a boiling point above say 93°C.
  • the oil may be a fatty alcohol-ether-ester complex derived from C10 alcohol distillation; it may be one selected from the paraffinic series, it may be an aromatic oil (e.g. naphthenic oil) or it may be any mixture of these.
  • the oil species that are possible, as equivalents, would represent an almost endless list and our broad-based examples, though few in number, are intended to emphasize this feature of the invention.
  • the most preferred embodiment is a solution of tall oil fatty acid in a C10 alcohol distillation residue as the oil carrier, in the weight proportion of about 15: 85, the dosage being about 20 mg/l.
  • the next preferred embodiment is tall oil fatty acid (surfactant) in naphthenic oil as the oil carrier, in the weight proportion of 15: 85 and the dosage being about 20 mg/l.
  • the preferred oil carrier (fatty acid solvent) is the C10 alcohol distillation residue having a boiling point of about 250°C. It is light yellow to yellowish brown in color and has a specific gravity of 0.862, OH ⁇ number 90, SAP No. 50, weight percent acetic 0.07 and carbonyl 0.5. Its main source (and commercial description) is the distallation bottoms or resident from distilling a C10 alcohol.
  • the green or pregnant liquor (charge) employed for alumina trihydrate precipitation is the hot caustic solution obtained after elimination of the red mud in the Bayer process. It is not necessary to an understanding of this invention to outline the whole Bayer process to those having skill in that art.
  • the green liquor, after red mud separation, is a hot, caustic filtrate, the commercial production green liquor containing the aluminum values as dissolved sodium aluminate.
  • This liquor and recirculated fine particle alumina trihydrate seeds are charged into a suitable precipitating tank or a series of connecting tanks.
  • the charge is cooled under agitation to stress the contents, causing precipitation of alumina hydrate crystals on the seeds which constitute growth sites.
  • the precipitation process involves nucleation followed by (a) initial crystal growth and (b) agglomeration of those crystals into a coarse or sandlike alumina trihydrate particle which will later be dried, and often calcined to obtain Al2O3 as the commercial product of value.
  • oil carrier is the alcohol distillation residue identified above, and the "fatty acid” is tall oil. Percents are weight percent.
  • the object of Examples 1A, 1B and 1C was to determine the response using different dosages of fatty acid/oil blend with different seed charges imposed on the green liquor of Plant A.
  • Response in all examples is the percent reduction to the ⁇ 44 ⁇ m fraction of the aluminum hydrate crystal. The greater the reduction, up to a limit, the better the performance in producing the large size crystals for calcination.
  • the "blank" in all examples is an undosed green liquor from the plant site.
  • Example 1C shows a coarser seed particle has no adverse effect on the present treatment; compare Example 1A, "fine seed.”
  • Examples 1D and 1E verify that beneficial results in percent reduction are achieved with different plant processes for precipitation, different seed charges and different tall oil purity.
  • the oil carrier is paraffinic, (b.p 150°C or higher), performing every bit as well as the C10 alcohol distillation residue.
  • the object of the following example (2A) was to determine the benefit, if any, using different ratios of fatty acid and oil carrier, compared to the fatty acid employed by itself as a treatment.
  • the fatty acid in this example was unrefined tall oil.
  • the object of the following example is to determine if beneficial results are obtained regardless of the order in which the components are added.
  • the fatty acid was refined tall oil.
  • Example 5A which follows, was to determine any synergistic effect of the fatty acid/oil blend compared to each separate component by itself.
  • the tall oil fatty acid by itself gives inferior performance compared to the paraffinic oil by itself (which gives nothing more than a nul result, the same as the Blank) but as will be shown by Examples 6A and 6B many different species of fatty acids are effective when combined with an oil carrier.
  • Example 6B the fatty acids of the first three compositions tested were respectively a tall oil with low rosin content, one with high rosin content and one with a high content of pitch, none of which made any appreciable or noteworthy difference.
  • all the acids are equated to the fatty acid class because the alkenyl succinic anhydrides hydrolyse in the Bayer pregnant liquor to alkenyl (dicarboxylic) fatty acid.
  • the examples are intended to demonstrate that the useful surfactants cover a wide range of chemical variants with or without attached functional groups which may contribute more surface activity to the surfactant compound. Therefore, many equivalents may be employed to supplant tall oil as long as the surfactant will disperse the oil in the hot caustic Bayer green liquor.
  • the oil as noted, is a high boiling point solvent for the surfactant and again there is a wide range of equivalents for the preferred species which is the distillation bottoms from distilling a C10 alcohol by oxy processing.
  • the treatment to shift or bias precipitation of alumina trihydrate crystals toward the coarser size is a surfactant combined with an oil.
  • the oil itself is a solvent for the surfactant, with a boiling point well above the temperature prevailing during precipitation, while the surfactant in turn is a dispersant or emulsifier for the oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Lubricants (AREA)
EP88105315A 1987-04-09 1988-03-31 Use of surfactants in alumina precipitation in the bayer process Expired - Lifetime EP0286034B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/036,389 US4737352A (en) 1987-04-09 1987-04-09 Use of surfactants in alumina precipitation in the bayer process
US36389 1987-04-09

Publications (2)

Publication Number Publication Date
EP0286034A1 EP0286034A1 (en) 1988-10-12
EP0286034B1 true EP0286034B1 (en) 1991-03-20

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ID=21888347

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EP88105315A Expired - Lifetime EP0286034B1 (en) 1987-04-09 1988-03-31 Use of surfactants in alumina precipitation in the bayer process

Country Status (11)

Country Link
US (1) US4737352A (es)
EP (1) EP0286034B1 (es)
JP (1) JPS6414111A (es)
CN (1) CN1016866B (es)
AU (1) AU593987B2 (es)
BR (1) BR8801621A (es)
CA (2) CA1266365A (es)
DE (2) DE3862052D1 (es)
ES (1) ES2010966B3 (es)
HU (1) HU202789B (es)
YU (1) YU46453B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7767190B2 (en) 1998-09-25 2010-08-03 Bhp Billiton Worsley Alumina Pty Ltd. Inhibiting the formation of TCA in a Bayer causticisation process

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE68910823T2 (de) * 1988-06-30 1994-03-17 Ind Minerals Res & Dev Entwässerung von Aluminiumtrihydrat und Entwässerungsmittel.
US5106599A (en) * 1990-02-06 1992-04-21 Nalco Chemical Company Alumina crystal growth additive
DE4039053A1 (de) * 1990-12-07 1992-06-11 Henkel Kgaa Polyglycerine im bayer-prozess
ATE149971T1 (de) * 1992-12-14 1997-03-15 Nalco Chemical Co Änderung der trihydrat-kristalle im bayer- verfahren
CA2126914A1 (en) * 1993-06-30 1994-12-31 Gillain Mary Moody Production of alumina
JP2784882B2 (ja) * 1994-04-28 1998-08-06 第一工業製薬株式会社 粉末状高融点２，２−ビス［４′−（２″，３″−ジブロモプロポキシ）−３′，５′−ジブロモフェニル］プロパンの製造方法
US5607598A (en) * 1995-07-14 1997-03-04 Ormet Corporation Treatment and disposal of red mud generated in the Bayer Process
US6293973B1 (en) 1996-10-11 2001-09-25 Nalco Chemical Company Method of controlling oxalate precipitation in bayer process liquor
US5902560A (en) * 1997-08-28 1999-05-11 Nalco Chemical Company Method for inhibiting precipitation of sodium oxalate in a Bayer process liquor
GB9800855D0 (en) 1998-01-15 1998-03-11 Allied Colloids Ltd Production of alumina
AU2004201629B2 (en) * 1998-09-25 2006-07-13 South32 Worsley Alumina Pty Ltd Improved bayer causticisation
DE10113294A1 (de) * 2001-03-16 2002-09-19 Stockhausen Chem Fab Gmbh Bildung von Aluminiumoxidhydrat-haltigen Kristallen aus kaustischen Mutterlaugen
US8971913B2 (en) * 2003-06-27 2015-03-03 Qualcomm Incorporated Method and apparatus for wireless network hybrid positioning
US7976821B2 (en) * 2005-06-23 2011-07-12 Nalco Company Composition and method for improved aluminum hydroxide production
US7976820B2 (en) * 2005-06-23 2011-07-12 Nalco Company Composition and method for improved aluminum hydroxide production
US7955589B2 (en) * 2005-06-23 2011-06-07 Nalco Company Composition and method for improved aluminum hydroxide production
CN100411989C (zh) * 2006-01-23 2008-08-20 中国铝业股份有限公司 三水铝石的溶出方法
US8628737B2 (en) * 2006-11-09 2014-01-14 Nalco Company Transfer of slurry in a bayer process
US7771681B2 (en) 2006-12-29 2010-08-10 Nalco Company Method for improved aluminum hydroxide production
US8282689B2 (en) * 2009-07-01 2012-10-09 Nalco Company Composition and method for enhancing the production of crystal agglomerates from a precipitation liquor
US9102995B2 (en) 2010-08-09 2015-08-11 Nalco Company Cross-linked ethylsulfonated dihydroxypropyl cellulose
US9199855B2 (en) 2010-08-09 2015-12-01 Nalco Company Chemical treatment to improve red mud separation and washing in the bayer process
US8298508B2 (en) 2010-08-09 2012-10-30 Nalco Company Recovery of alumina trihydrate during the bayer process using cross-linked polysaccharides
CN105073642B (zh) * 2013-03-13 2017-06-20 纳尔科公司 交联的乙基磺化二羟丙基纤维素
US8920768B2 (en) * 2013-03-14 2014-12-30 Ecolab Usa Inc. Crystallization aids for bayer aluminum hydroxide
US9896366B2 (en) * 2014-02-26 2018-02-20 Ecolab Usa Inc. Alternative additives to enhance slurry dewatering
US9592456B2 (en) * 2015-02-11 2017-03-14 Ecolab Usa Inc. Methods for enhancing production of aluminum hydroxide in an aluminum hydroxide production process
EA033081B1 (ru) 2015-03-11 2019-08-30 Сайтек Индастриз, Инк. Не содержащие масло модификаторы роста кристаллов для извлечения оксида алюминия
US10427950B2 (en) 2015-12-04 2019-10-01 Ecolab Usa Inc. Recovery of mining processing product using boronic acid-containing polymers
CN109843806A (zh) * 2016-09-09 2019-06-04 塞特工业公司 用于拜耳法的无油晶体生长调节剂

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Publication number Priority date Publication date Assignee Title
DE636707C (de) 1933-07-26 1936-10-15 Chemische Fabriken Akt Ges Gam Verfahren zur Ausfaellung von Tonerdehydrat aus Alkalialuminatloesungen
US2440378A (en) * 1946-09-13 1948-04-27 Aluminum Co Of America Treatment of sodium aluminate solutions
ZA713178B (en) * 1971-05-17 1972-01-26 Nalco Chemical Co Continuous process for preparing extruded alumina bodies
US4578255A (en) * 1984-12-27 1986-03-25 Kaiser Aluminum Chemical Corporation Purification of Bayer process liquors
US4608237A (en) * 1985-04-24 1986-08-26 Nalco Chemical Company Use of polymers in alumina precipitation in the Bayer process of bauxite beneficiation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7767190B2 (en) 1998-09-25 2010-08-03 Bhp Billiton Worsley Alumina Pty Ltd. Inhibiting the formation of TCA in a Bayer causticisation process

Also Published As

Publication number Publication date
US4737352A (en) 1988-04-12
YU46453B (sh) 1993-10-20
CN1016866B (zh) 1992-06-03
CA1275889C (en) 1990-11-06
AU593987B2 (en) 1990-02-22
HUT46597A (en) 1988-11-28
ES2010966B3 (es) 1991-10-16
DE3862052D1 (de) 1991-04-25
DE286034T1 (de) 1989-12-28
ES2010966A4 (es) 1989-12-16
AU1401788A (en) 1988-10-13
YU71088A (en) 1990-02-28
HU202789B (en) 1991-04-29
CA1266365A (en) 1990-03-06
EP0286034A1 (en) 1988-10-12
CN88101926A (zh) 1988-10-26
JPS6414111A (en) 1989-01-18
BR8801621A (pt) 1988-11-08

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